2-Oxabicyclooctane derivatives, processes for preparing same and organoleptic uses thereof

ABSTRACT

Described are derivatives of 2-oxabicyclo[2.2.2]octanes and precursors therefor, cyclohexenemethanols as well as lower alkyl esters of said cyclohexenemethanols. The oxabicyclooctanes are useful in perfumery and foodstuff, medicinal product and tobacco flavors. The cyclohexenemethanols are useful as precursors for the oxabicyclooctanes and are, themselves, useful for their organoleptic properties in perfumery and flavors as are the esters of said cyclohexenemethanols.

This application is a divisional of application for United StatesLetters Patent Ser. No. 046,936 filed on June 7, 1979, now U.S. Pat. No.4,231,940 issued on Nov. 4, 1980 which in turn is a divisional ofapplication for United States Letters Patent Ser. No. 953,128 filed onOct. 20, 1978, now U.S. Pat. No. 4,195,099 issued on Mar. 25, 1980.

BACKGROUND OF THE INVENTION

The instant invention provides novel oxabicyclooctanes having thestructure: ##STR1## wherein R₁ is hydrogen or methyl and R₂ is one of C₃-C₅ alkyl or alkenyl as well as intermediates for producing same havingthe generic structure: ##STR2## wherein R₁ is hydrogen or methyl, R₂ isone of C₃ -C₅ alkyl or alkenyl and one of the dashed lines is acarbon-carbon double bond and the other of the dashed lines is acarbon-carbon single bond, and C₁ -C₃ alkyl esters thereof, and usedthereof for their organoleptic properties in consumable materials.

Chemical compounds which can provide green, minty, herbaceous (e.g.,rosemary, garden mint, thyme and wet lettuce) cooling, sweet, fruity,woody, eucalyptol-like, buchu-like, caraway, spicey, carvone-like,minty, basil-like, sweet anise, peppery and geranium-like aromas withfruity, blueberry-like nuances are desirable in the art of perfumery.Many of the natural materials which provide such fragrances andcontribute such desired nuances to perfumery compositions are high incost, unobtainable at times, vary in quality from one batch to anotherand/or are generally subject to the usual variations of naturalproducts.

By the same token, materials which can provide dill, parsley-like,nutmeg-like, celery-like, floral, lemon, grapefruit-like, carrot-like,raisin-like, woody, safranal-like, piney, strawberry-like,raspberry-like, blueberry-like, spicey, herbaceous, lime-like, blacktea-like, black pepper-like, fennel, anise-like, licorice-like, green,sassafras-like, minty, juicy fruit, orange-like, sweet, floral, fruity,berry-like aromas and dill, parsley-like, nutmeg, celery-like, lemon,grapefruit-like, carrot-like, woody, raisin-like, tobacco-like, piney,spicey, strawberry-like, raspberry-like, blueberry-like, spicey,herbaceous, lime-like, black tea-like, black pepper, biting, sweet,fennel, anise-like, licorice-like, green, sassafras-like, minty,juicyfruit-like, orange-like, floral, fruity, berry-like and herbaceousflavor characteristics are desirable in applying the art of flavoring tofoodstuffs, toothpastes, chewing gums and medicinal products. Many ofthe natural materials which provide such flavor notes and contributedesired nuances to flavoring compositions are high in cost, vary inquality from one batch to another and/or are generally subject to theusual variations of natural products.

By the same token, hay, fruity, herbaceous aromas prior to and onsmoking are desirable in the tobacco art for enhancing naturaltobacco-like notes.

There is, accordingly, a continuing effort to find synthetic materialswhich will replace, enhance or augment the essential flavor andfragrance notes provided by natural essential oils or compositionsthereof. Unfortunately, many of these synthetic materials either havethe desired nuances only to a relatively small degree or else contributeundesirable or unwanted odor to the compositions. The search formaterials which can provide a more refined root beer-like flavor, forexample, has been difficult and relatively costly in the areas of bothnatural products and synthetic products.

Artificial flavoring agents for foodstuffs have received increasingattention in recent years. For many years, such food flavoring agentshave been preferred over natural flavoring agents at least in part dueto their diminished cost and their reproducible flavor qualities. Forexample, natural food flavoring agents such as extracts, concentratesand the like are often subject to wide variations due to changes inquality, type and treatment of the raw materials. Such variations can bereflected in the end products and result in unfavorable flavorcharacteristics in said end product. Additionally, the presence of thenatural product in the ultimate food may be undesirable because ofincreased tendency to spoil. This is particularly troublesome in foodand food uses where such products as dips, soups, chips, sausages,gravies and the like are apt to be stored prior to use.

The fundamental problem in creating artificial flavor agents is that theartificial flavor to be achieved be as natural as possible. Thisgenerally proves to be a difficult task since the mechanism for flavordevelopment in many foods, medicinal products, chewing gums andtoothpastes is not completely known. This is noticeable in productshaving licorice, spice, dill, parsely, carrot, grapefruit, nutmeg,spearmint, lemon juice, lime, blueberry, raspberry, strawberry, blackpepper, and root beer flavor characteristics, particularly.

Even more desirable are products that can serve to substitute fordifficult-to-obtain natural perfumery oils and at the same timesubstitute for natural flavoring ingredients in foodstuffs, chewinggums, medicinal products and toothpastes and in addition, at the sametime, substitute for natural flavoring ingredients in tobaccos.

Arctander in "Perfume and Flavor Chemicals (Aroma Chemicals)", Vol. I,1969 at monograph No. 616 describes 1,8-cineole having the structure:##STR3## as being useful in perfumery and in flavor compositions.

Thus, Arctander states, regarding 1,8-cineole:

"Fresh, diffusive, camphoraceous-cool odor of poor tenacity. Sweet andfresh, cool-camphoraceous taste and cool mouthfeel unless very highlyconcentrated.

Widely used in perfume compositions for its refreshing effect inherbaceous type fragrances, Lavender, New Mown Hay, Fougere, etc. and inmedicinal type odors for soap and household products. Also, in maskingodors for industrial purposes, unless Eucalyptus oil must be used forits lower cost.

This oxide has found increased usage during the 1965/66 period ofabnormally high prices for Lavandin and Spike Lavender oils.

The odor of Eucalyptus is, in some countries, rated synonomous withmasking odors for lavatories, etc., a fact which has an unquestionablepsychological effect, causing people to reject the odor of Eucalyptusfor oral-hygienic purposes, etc. Similar viewpoints has been observedabout the use of Methylsalicylate in dentrifrice in many Europeancountries. Peculiarly enough, Methylsalicylate is still a popularcandy-, soft-drink- and toothpaste flavor in the U.S.A., where the esterat the same time is used as a masking agent in toilet-bowl cleaners!

The `olfactory association` is quite human and common, but it may attimes completely destroy the chances of a chemical from its use inflavors or other field.

Eucalyptol is extensively used in flavor compositions, particularly inall types of preparations for oral hygiene, dentifrice, breath-sprays,mouthwashes, cough lozenges, pastilles, skin-rubbing lotions, inhalatorfluids, etc .

It seems, however, that its use in skin rubbing lotions has hampered itspopularity as a candy flavor in the U.S.A.

Normal use concentrations are about 1 to 15 ppm in the finished(flavored) product, but concentrations as high as 200 ppm are found inchewing gum."

Furthermore, the compound having the structure: ##STR4## and thecompound having the structure: ##STR5## are reported by Sopov and Kovnerat Zh. Obsch. Khim. 34, 1492-6 (1964) as abstracted in Chem. Abstracts,Vol. 61, 5529b.

The Sopov and Kovner reference does not, however, disclose organolepticuses of the compounds having the structures: ##STR6##

Furthermore, nothing in the prior art discloses any of the compoundshaving the generic structure: ##STR7## wherein R₂ is C₃ -C₅ alkyl oralkenyl and R₁ is hydrogen or methyl and nothing in the prior artdiscloses organoleptic uses or uses as intermediates of the compoundhaving the structure: ##STR8## wherein R₁ is hydrogen or methyl and R₂is C₃ -C₅ alkyl or alkenyl, or lower alkyl esters thereof, e.g.,acetates.

Insofar as their organoleptic uses are concerned, the compounds of theinstant invention have unexpected, unobvious and advantageous propertiesover such compounds of the prior art as 1,8-cineole.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the product produced according to ExampleIA.

FIG. 2 is the NMR spectrum for the product produced according to ExampleIA.

FIG. 3 is the infra-red spectrum for the product produced according toExample IA.

FIG. 4 is the GLC profile for the oxabicyclooctane produced according toExample IB.

FIG. 5 is the NMR spectrum for the product produced according to ExampleIB.

FIG. 6 is the infra-red spectrum for the product produced according toExample IB.

FIG. 7 is the GLC profile for the product produced according to ExampleII.

FIG. 8 is the NMR spectrum for fraction 4 of the final product ofExample II, the 1-methyl-3-(2-methylpropyl)-2-oxabicyclo[2.2.2]octane.

FIG. 9 is the infra-red spectrum for fraction 4 of the oxabicyclooctaneproduced according to Example II.

FIG. 10 is the GLC profile for the product produced according to ExampleIII.

FIG. 11 is the NMR spectrum for the product produced according toExample III.

FIG. 12 is the infra-red spectrum for the product produced according toExample III.

FIG. 13 is the NMR spectrum for the product produced according toExample IV.

FIG. 14 is the infra-red spectrum for the product produced according toExample IV.

FIG. 15 is the NMR spectrum for the product produced according toExample V(A).

FIG. 16 is the infra-red spectrum for the product produced according toExample V(A).

FIG. 17 is the NMR spectrum for the product produced according toExample V(B).

FIG. 18 is the infra-red spectrum produced according to the process ofExample V(B).

FIG. 19 is the GLC profile for the product produced according to ExampleVI(A).

FIG. 20 is the GLC profile for the product produced according to ExampleVI(B).

FIG. 21 is the infra-red spectrum for the product produced according toExample VI(B), the 3-butyl-2,5-dimetyl-2-oxabicyclo[2.2.2]octane.

FIG. 22 is the GLC profile for the product produced according to ExampleVII(A).

FIG. 23 is the NMR spectrum for the product produced according toExample VII(A).

FIG. 24 is the infra-red spectrum for the product produced according toExample VII(A).

FIG. 25 is the GLC profile (5 hours) for the product produced accordingto Example VII(B).

FIG. 26 is the NMR spectrum for the product produced according toExample VII(B).

FIG. 27 is the infra-red spectrum for the product produced according tothe process of Example VII(B).

FIG. 28 is the GLC profile for the product produced according to ExampleVIII.

FIG. 29 is the NMR spectrum for the product produced according toExample VIII.

FIG. 30 is the infra-red spectrum for the product produced according tothe process of Example VIII.

FIG. 31 is the GLC profile for the product produced according to theprocess of Example IX.

FIG. 32 is the NMR spectrum for the product produced according to theprocess of Example IX.

FIG. 33 is the infra-red spectrum for the product produced according tothe process of Example IX.

FIG. 34 is the GLC profile for the product produced according to ExampleX.

FIG. 35 is the NMR spectrum (fraction 7) for the product producedaccording to the process of Example X.

FIG. 36 is the infra-red spectrum (fraction 7) for the product producedaccording to the process of Example X.

FIG. 37 is the NMR spectrum for fraction 4 of the reaction productproduced according to Example XXXII.

FIG. 38 is the infra-red spectrum for fraction 4 of the reaction productproduced according to Example XXXII.

FIG. 39 is the GLC profile for the reaction product produced accordingto Example XXXIII.

FIG. 40 is the NMR spectrum for the reaction product produced accordingto Example XXXIII.

FIG. 41 is the infra-red spectrum for the reaction product producedaccording to Example XXXIII.

FIG. 42 is the GLC profile for the crude reaction product producedaccording to Example XXXIV.

FIG. 43 is the NMR spectrum for fraction 6 of the reaction productproduced according to Example XXXIV.

FIG. 44 is the infra-red spectrum for fraction 6 produced according toExample XXXIV.

THE INVENTION

It has now been determined that certain oxabicyclooctanes as well ascertain precursors therefor which are cyclohexene alkyl and alkenylcarbinols and their esters are capable of imparting a variety of flavorsand fragrances to various consumable materials and are also capable ofaugmenting or enhancing a variety of flavors and fragrances of variousconsumable materials.

Briefly, our invention contemplates augmenting or enhancing the flavorsand/or fragrances of such consumable materials as perfumes, perfumedarticles, colognes, foodstuffs, chewing gums, toothpastes, medicinalproducts and smoking tobaccos by adding thereto a small but effectiveamount of at least one of the compounds having one of the genericstructures: ##STR9## wherein R₁ is hydrogen or methyl; R₂ is C₃ -C₅alkyl or alkenyl; R₅ is hydrogen or C₁ -C₄ acyl; and one of the dashedlines is a carbon-carbon single bond and the other of the dashed linesis a carbon-carbon double bond.

The oxabicyclooctane derivatives and the cyclohexene alkyl and alkenylcarbinols and esters thereof our our invention augment or enhance dill,parsley, nutmeg, celery-like, floral, lemon, raisin-like, woody,saffranal-like, piney, strawberry-like, raspberry-like, blueberry-like,carrot-like, grapefruit-like, spicey, herbaceous, lime, black tea-like,black pepper, fennel, anise-like, licorice-like, green, sassafras-like,minty, juicyfruit, orange-like, sweet, floral, fruity, berry-like, andherbaceous aroma characteristics, and dill, parsley, nutmeg,celery-like, lemon, woody, raisin-like, carrot-like, grapefruit-like,tobacco-like, piney, spicey, strawberry-like, raspberry-like,blueberry-like, spicey, herbaceous, lime, black tea-like, black pepper,biting, sweet, fennel, anise-like, licorice-like, green, sassafras-like,minty, juicy-fruit-like, orange-like, floral, fruity, berry-like, andherbaceous flavor characteristics insofar as augmenting or enhancing thearoma or taste of foodstuffs, toothpastes, medicinal products andchewing gum.

The oxabicyclooctane derivatives and the cyclohexene alkyl and alkenylcarbinols and esters thereof of our invention also augment or enhancethe green, minty, herbaceous (e.g., rosemary, garden mint, thyme and wetlettuce), cooling, sweet, fruity, woody, eucalyptol, buchu-like,caraway-like, spicey, carvone-like, basil-like, sweet anise-like,peppery and geranium aromas of perfumes, perfumed articles and colognesof our invention.

The oxabicyclooctane derivatives and the cyclohexene alkyl and alkenylcarbinols and esters thereof of our invention also augment or enhancethe natural tobacco-like characteristics of smoking tobacco by impartingthereto hay, fruity and herbaceous aroma and taste nuances prior to andon smoking in the main stream and in the side stream.

Examples of the oxabicyclooctane derivatives and the cyclohexene alkyland alkenyl carbinols and esters thereof our invention and theirorganoleptic characteristics are as follows:

    __________________________________________________________________________    STRUCTURE OF                                                                  COMPOUND      NAME OF COMPOUND                                                                           FLAVOR CHARACTERISTICS                                                                         FRAGRANCE CHARACTERISTICS         __________________________________________________________________________     ##STR10##    1,5-Dimethyl-3- isopropyl-2-oxa- bicyclo[2.2.2] octane                                     A lime, lemon, rasin-like, woody, and                                         saffronal-like aroma with lime, lemon, woody,                                 rasin-like and tobacco-like flavor characterist                               ics.             A green, minty, herbaceous                                                    (rosemary) aroma with a                                                       cooling effect.                    ##STR11##    1-methyl-3-(2- methylpropyl)-2- oxabicyclo[2.2.2] octane                                   A dill, parsley-like, nutmeg-like. celery-like                                roma with dill, parsley- like, nutmeg-like and                                elery-like flavor nuances.                          ##STR12##    3-allyl-1-methyl- 2-oxabicyclo[2.2.2] octane                                               A herbaceous. piney, spicey, strawberry-like,                                 raspberry-like, and blue- berry-like aroma                                    character- istics with herbaceous, piney,                                     spicey, strawberry- like, raspberry-like and                                  blueberry-like flavor characteristics.                                                         A minty, eucalyptol-like,                                                     herbaceous (garden mint,                                                      thyme), buchu-like aroma with                                                 caraway-like nuances.              ##STR13##    3-n-butyl-2,5- dimethyl-2-oxa- bicyclo[2.2.2] octane                                       A spicey, black pepper- like, herbaceous, lime                                nd black tea aroma with spicey, black pepper-                                 like, herbaceous, lime and black tea-like                                     flavor nuances.  A green, spicey, carvone-like                                                 roma.                              ##STR14##    1,5-dimethyl-3- n-propyl-2-oxa- bicyclo[2.2.2] octane                                      A black pepper and spicey aroma with black                                    pepper, spicey and biting flavor characteristic                               s.               A herbaceous, minty (garden                                                   mint) aroma with basil, thyme                                                 and caraway nuances.               ##STR15##    1,5-dimethyl-3- n-pentyl-2-oxa- bicyclo[2.2.2] octane                                      A woody, spicey and black pepper aroma with                                   black pepper flavor character- istics insofar                                 as food- stuffs are concerned. Insofar as                                     tobacco uses are concerned, imparts a hay,                                    fruity and herbaceous characteristic and                                      enhances the natural tobacco notes prior to                                   and on smoking insofar as smoking tobacco is                                  concerned.       An oily, green, herbaceous                                                    (wet lettuce) aroma.               ##STR16##    α-allyl-4-methyl- 3-cyclohexene- methanol                                            A sweet, fennel, anise- like, licorice-like                                   and green aroma character- istic with sweet,                                  fennel, anise-like, licorice- like and green                                  flavor characteristics.                                                                        A sweet, anise, carvone- like                                                 and minty aroma.                   ##STR17##    2,4-dimethyl-α- allyl-3-cyclo- hexenemethanol                                        A sweet, floral, licorice- like, fruity,                                      berry-like, herbaceous, and green aroma with                                  sweet, floral, licorice-like,                                                 fruity, berry-like, herbaceous and green                                      flavor character- istics.                                                                      A sweet, anisic, citrus aroma                                                 ith minty, peppery, and                                                       geranium-like undertones.          ##STR18##    2,4-dimethyl-α- isopropyl-3- cyclohexene-1- methanol                                 A sassafras-like, minty, juicy fruit and                                      orange- like aroma with sassafras- like,                                      minty, juicy fruit- like and orange-like                                      flavor characteristics.                             ##STR19##    α-allyl-4-methyl- 3-cyclohexene- 1-methanol                                          A green, oriental, floral aroma character with                                green, floral and bitter flavor characteristics                               .                A sweet, fruity, herbaceous,                                                  floral aroma with carvone-                                                    like and geranyl acetate-like                                                 uances.                            ##STR20##    4,6-dimethyl-α- allyl-3-cyclo- hexenemethanol                                        A sweet, floral, licorice- like, fruity,                                      berry-like, herbaceous and green aroma                                        characteristic with sweet, floral, licorice,                                  fruity, berry, herbaceous and green flavor                                    character- istics.                                                                             A sweet, herbaceous, fruity                                                   aroma with basil and                                                          blueberry- like undertones.        ##STR21##    α-allyl-4,6- dimethyl-3-cyclo- hexene-1-methanol                        acetate      A green, spicey, floral aroma characteristic                                  with biting flavor character- istics at 2                                                      A green, fruity, anisic,                                                      woody  aroma.                      ##STR22##                 A weedy green, grape- fruit-like, carrot-like                                 aroma with a weedy green, grapefruit,                                         carrot-like flavor at 3.0 ppm.                                                                 A green, floral, minty,                                                       lemonly aroma.                    __________________________________________________________________________

The oxabicyclooctane derivatives and the cyclohexene alkyl and alkenylcarbinols and esters thereof of our invention can be produced by firstforming a cyclohexene carboxaldehyde by reaction of an α,β-unsaturatedaldehyde with a conjugated diene. The resulting cyclohexenecarboxaldehyde is then reacted with a Grignard reagent to form anorganometallic salt of a cyclohexene carbinol. The organometallic saltof the cyclohexene carbinol is then hydrolyzed (in the presence of acid)to form a cyclohexene carbinol of our invention. This reaction productmay be used as is for its organoleptic properties or either (i) it maybe further reacted by cyclizing the compound to form the desired2-oxabicyclo[2.2.2]octane or (ii) it may be esterified with a C₁ -C₄acyl halide or acyl anhydride such as acetyl chloride or aceticanhydride. The over-all reaction sequence described above is as follows:##STR23## wherein R₁ and R₃ each represent hydrogen or methyl and areeach the same or different; wherein R₄ is hydrogen, methyl or ethyl;wherein R₂ is one of C₁ -C₆ alkyl or one of C₃ -C₅ alkenyl; wherein R₆is hydrogen, methyl or ethyl; and wherein one of the dashed lines is acarbon-carbon double bond and the other of the dashed lines is acarbon-carbon single bond; and where X is chloro, bromo or iodo.

The reaction scheme of our invention may be further exemplified and morespecifically set forth insofar as it forms the novel compounds of ourinvention as follows: ##STR24## wherein one of the dashed lines is acarbon-carbon double bond and the other of the dashed lines is acarbon-carbon single bond; wherein R₁ is hydrogen or methyl; wherein R₂is one of C₃ -C₅ alkyl or alkenyl; wherein R₆ is hydrogen, methyl orethyl; and wherein X is one of chloro, bromo or iodo.

The Diels-Alder reaction of the α,β-unsaturated aldehyde with theconjugated diene is a procedure well known in the prior art. Thereaction may be carried out in the presence of Lewis acid catalysts suchas zinc chloride, aluminum chloride or aluminum bromide; or it may becarried out in the absence of catalysts at higher temperatures, e.g.,50° C. up to 150° C. When carrying out the Diels-Alder reaction in thepresence of catalysts, lower temperature, e.g., -10° C. up to 30° C. maybe utilized.

That part of the reaction sequence whereby the cyclohexenecarboxaldehyde is reacted with the Grignard reagent to form thecyclohexene carbinol organometallic salt followed by hydrolysis of thecyclohexene carbinol organometallic salt to form the cyclohexenecarbinol followed by cyclization of the resulting cyclohexene carbinolto form the 2-oxabicyclo[2.2.2]octane may be carried out either in onestep or in two steps.

In carrying out the "two-step reaction" whereby the cyclohexene carbinolis first isolated and then cyclized in the first step, that is, in thereaction of the Grignard reagent with the cyclohexene carboxaldehyde,the mole ratio of alkyl halide or alkenyl halide to magnesium in orderto form the Grignard reagent is from 0.9:1 up to 1.5:1. The mole ratioof alkyl halide or alkenyl halide to cyclohexene carboxaldehyde is from0.8:1 up to 1.5:1. This reaction of the Grignard reagent with thecyclohexene carboxaldehyde takes place in an ether solvent such asdiethyl ether, tetrahydrofuran or di-n-butyl ether or another inertsolvent such as toluene, chloroform or benzene to which two equivalentsof ether has been added. The temperature of reaction preferably isbetween 0° and 100° C. with the most preferred temperature range forthis reaction being from 35° C. up to 45° C.

In the two-step reaction, the resulting cyclohexene carbinol is thenisolated as by distillation. The resulting cyclohexene carbinol is thencyclized at a temperature in the range of from 25° C. up to 150° C. inthe presence of an acid such as aqueous hydrochloric acid or sulfuricacid or phosphoric acid. This acid may be used in combination with analcohol such as isopropyl alcohol or with some other solvents such astetrahydrofuran or acrylonitrile or the acid may be used by itself toeffect the cyclization. The cyclization in the alternative may becarried out using a Lewis Acid such as borotrifluoride, aluminumtrichloride, zinc chloride, stannic chloride, or zinc bromide in thepresence of a solvent such as toluene, chloroform or xylene.

As stated above, the reaction of the cyclohexene carboxaldehyde to formthe cyclohexene carbinol followed by cyclization may take place in asingle reactor without separation of the cyclohexene carbinol. Theconditions are the same as stated above for the two-step reaction.

If desired, the cyclohexene carbinol may be acylated rather thancyclized whereby esters useful for their organoleptic properties areformed. Suitable acrylating reagents are acidic anhydride, acetylchloride, propionic anhydride and propionyl chloride. The acylation iscarried out under standard acylating conditions known to those havingordinary skill in the art, e.g., -10° C.-50° C. in the presence in aninert solvent, e.g., toluene or xylene.

The individual oxabicyclooctane derivatives and the cyclohexene alkyland alkenyl carbinols and esters of our invention can be obtained inpure form or in substantially pure form by conventional purificationtechniques. Thus, the products can be purified and/or isolated bydistillation, extraction, crystallization, preparative chromatographictechniques (column chromatography and vapor phase chromatography) andthe like. It has been found desirable to purify the oxacyclooctanederivatives and the cyclohexene alkyl and alkenyl carbinols and estersof our invention by fractional distillation in vacuo.

When the oxabicyclooctane derivatives and the cyclohexene alkyl andalkenyl carbinols and esters of our invention are used as food flavoradjuvants, the nature of the co-ingredients included with saidoxabicyclooctane derivatives and the cyclohexene alkyl and alkenylcarbinols and esters in formulating the product composition will alsoserve to alter, modify, augment or enhance the organolepticcharacteristics of the ultimate foodstuff treated therewith.

As used herein in regard to flavors, the terms "alter", "modify" and"augment" in their various forms means "supplying or imparting flavorcharacter or note to otherwise bland, relatively tasteless substances oraugmenting the existing flavor characteristic where a natural flavor isdeficient in some regard or supplementing the existing flavor impressionto modify its quality, character or taste".

The term "enhance" is used herein to mean the intensification of aflavor or aroma characteristic or note without the modification of thequality thereof. Thus, "enhancement" of a flavor or aroma means that theenhancement agent does not add any additional flavor note.

As used herein, the term "foodstuff" includes both solid and liquidingestible materials which usually do, but need not, have nutritionalvalue. Thus, foodstuffs include soups, convenience foods, beverages,dairy products, candies, vegetables, cereals, soft drinks, snacks, andthe like.

As used herein, the term "medicinal product" includes both solids andliquids which are ingestible, non-toxic materials which have medicinalvalue such as cough syrups, cough drops, aspirin and chewable medicinaltablets.

The term "chewing gum" is intended to mean a composition which comprisesa substantially water insoluble, chewable plastic gum base such aschicle, or substitutes therefor, including jelutong, guttakay, rubber orcertain comestible natural or synthetic resins or waxes. Incorporatedwith the gum base in admixture therewith may be plasticizers orsoftening agents, e.g., glycerine, and a flavoring composition whichincorporates one or more of the oxabicyclooctane derivatives and thecyclohexene alkyl and alkenyl carbinols and esters of our invention, andin addition, sweetening agents which may be sugars, including sucrose ordextrose and/or artificial sweeteners such as cyclamates or saccharin.Other optional ingredients may also be present.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. It is a requirement that any suchmaterial be "ingestibly" acceptable and thus non-toxic and otherwisenon-deleterious particularly from an organoleptic standpoint whereby theultimate flavor and/or aroma of the consumable material used is notcaused to have unacceptable aroma and taste nuances. Such materials mayin general be characterised as flavoring adjuvants or vehiclescomprising, broadly, stabilizers, thickeners, surface active agents,conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride,antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole (mixture of 2- and 3-tertiary-butyl-4-hydroxyanisole), butylated hydroxytoluene (2,6-di-tertiary-butyl-4-methylphenol), propyl gallate and the like, and sequestrants, e.g., citricacid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar agar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials; lipids,carbohydrates; starches, pectins, and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g., sucrose, corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogn peroxide and the like;starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, tumeric and curcuma and thelike, firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tri-basic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acids, e.g.,acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovalericacid, alphamethylbutyric acid, propionic acid, valeric acid,2-methyl-2-pentenoic acid, and 2-methyl-3-pentenoic acid; ketones andaldehydes, e.g., acetaldehyde, acetophenone, acetone, acetyl methylcarbinol, acrolein, n-butanal, crotonal, diacetyl, 2-methylbutanal,beta,beta-dimethyl acrolein; methyl n-amyl ketone, n-hexanal, 2-hexenal,isopentanal, hydrocinnamic aldehyde, cis-3-hexenal, 2-heptenal, nonylaldehyde, 4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone,2-methyl-3-butanone, benzaldehyde, beta-damascone, alpha-damascone,beta-damascenone, acetophenone, 2-heptanone, o-hydroxy-acetophenone,2-methyl-2-hepten-6-one, 2-octanone, 2-undecanone, 3-phenyl-4-pentenal,2-phenyl-2-hexenal, 2-phenyl-2-pentenal, furfural, 5-methylfurfural,cinnamaldehyde, beta-cyclohomocitral, 2-pentanone, 2-pentenal andpropanal; alcohols such as 1-butanol, benzyl alcohol, 1-borneol,trans-2-buten-1-ol, ethanol, geraniol, 1-hexanol, 2-heptanol,trans-2-hexenol-1, cis-3-hexen-1-ol, 3-methyl-3-buten-1-ol, 1-pentanol,1-penten-3-ol, p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchylalcohol, phenyl-2-ethanol, alpha-terpineol, cis-terpinhydrate, eugenol,linalool, 2-heptanol, acetoin; esters, such as butyl acetate, ethylacetate, ethyl acetoacetate, ethyl benzoate, ethyl butyrate, ethylcaprate, ethyl caproate, ethyl carpylate, ethyl cinnamate, ethylcrotonate, ethyl formate, ethyl isobutyrate, ethyl isovalerate, ethyllaurate, ethyl myristate, ethyl alpha-methylbutyrate, ethyl propionate,ethyl salicylate, trans-2-hexenyl acetate, hexyl acetate, 2-hexenylbutyrate, hexyl butyrate, isoamyl acetate, isopropyl butyrate, methylacetate, methyl butyrate, methyl caproate, methyl isobutyrate,alpha-methylphenylglycidate, ethyl succinate, isobutyl cinnamate,cinnamyl formate, methyl cinnamate, and terpenyl acetate; hydrocarbonssuch as dimethyl naphthalene, dodecane, methyldiphenyl, meythylnaphthalene, myrcene, naphthalene, octadecane, tetradecane,tetramethylnaphthalene, tridecane, trimethylnaphthalene, undecane,caryophyllene, alphaphellandrene, beta-phellandrene, p-cymene1-alpha-pinene, beta-pinene, dihydrocarveol; pyrazines such as2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine,3-ethyl-2,5-dimethylpyrazine, 2-ethyl-3,5,6-trimethylpyrazine,3-isoamyl-2,5-dimethylpyrazine, 5-isoamyl-2,3-dimethylpyrazine,2-isoamyl-3,5,6-trimethylpyrazine, isopropyl dimethylpyrazine, methylethylpyrazine, tetramethylpyrazine, trimethylpyrazine; essential oilssuch as jasmine absolute, cassia oil, cinnamon bark oil, black pepperoleoresin, oil of black pepper, rose absolute, orris absolute, oil ofcubeb, oil of coriander, oil of pimento leaf, oil of patchouli, oil ofnutmeg, lemon essential oil, safran oil, Bulgarian rose, capsicum, yarayara and vanilla; lactones such as γ-nonalactone; sulfides, e.g., methylsulfide and other materials such as maltol, and acetals (e.g.,1,1-diethoxyethane, 1,1-dimethyloxyethane and dimethoxymethane),piperine, chavicine, and piperidine.

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural, and should, in any event,(i) be organoleptically compatable with the oxabicyclooctane derivativesand the cyclohexene alkyl and alkenyl carbinols and esters of ourinvention by not covering or spoiling the organoleptic properties (aromaand/or taste) thereof; (ii) be non-reactive with the oxabicyclooctenederivatives and the cyclohexene alkyl and alkenyl carbinols and estersof our invention and (iii) be capable of providing an environment inwhich the oxabicyclooctane derivatives and the cyclohexene alkyl andalkenyl carbinols and esters can be dispersed or admixed to provide ahomogeneous medium. In addition, selection of one or more flavoringadjuvants, as well as the quantities thereof will depend upon theprecise organoleptic character desired in the finished product. Thus, inthe case of flavoring compositions, ingredient selection will vary inaccordance with the foodstuff, chewing gum, medicinal product ortoothpaste to which the flavor and/or aroma are to be imparted,modified, altered or enhanced. In contradistinction, in the preparationof solid products, e.g., simulated foodstuffs, ingredients capable ofproviding normally solid compositions should be selected such as variouscellulose derivatives.

As will be appreciated by those skilled in the art, the amount ofoxabicyclooctane derivatives and the cyclohexene alkyl and alkenylcarbinols and esters employed in a particular instance can vary over arelatively wide range, depending upon the desired organoleptic effectsto be achieved. Thus, correspondingly, greater amounts would benecessary in those instances wherein the ultimate food composition to beflavored (e.g., with a spice flavor or a specific black pepper-likeflavor) is relatively bland to the taste, whereas relatively minorquantities may suffice for purposes of enhancing the composition merelydeficient in natural flavor or aroma. The primary requirement is thatthe amount selected be effective, i.e., sufficient to alter, modify orenhance the organoleptic characteristics of the parent composition,whether foodstuff per se, chewing gum per se, medicinal product per se,toothpaste per se, or flavoring composition.

The use of insufficient quantities of oxabicyclooctane derivatives andthe cyclohexene alkyl and alkenyl carbinols and esters will, of course,substantially vitiate any possibility of obtaining the desired resultswhile excess quantities prove needlessly costly and in extreme cases maydisrupt the flavor-aroma balance, thus proving selfdefeating.Accordingly, the terminology "effective amount" and "sufficient amount"is to be accorded a significance in the context of the present inventionconsistent with the obtention of desired flavoring effects.

Thus, and with respect to ultimate food compositions, chewing gumcompositions, medicinal product compositions and toothpastecompositions, it is found that quantities of bicyclooctane derivativesand the cyclohexene alkyl and alkenyl carbinols and esters ranging froma small but effective amount, e.g., 0.05 parts per million up to about500 parts per million based on total composition, are suitable.Concentrations in excess of the maximum quantity stated are not normallyrecommended since they fail to provide commensurate enhancement oforganoleptic properties. In those instances wherein the bicyclooctanederivatives and the cyclohexene alkyl and alkenyl carbinols and estersare added to the foodstuff as an integral component of a flavoringcomposition, it is of course, essential that the total quantity offlavoring composition employed be sufficient to yield an effectivebicyclooctane derivative and cyclohexene alkyl and alkenyl carbinol andester concentration in the foodstuff product.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the bicyclooctane derivatives andcyclohexene alkyl and alkenyl carbinols and esters in concentrationsranging from about 0.025% up to about 15% by weight based on the totalweight of the said flavoring composition.

The composition described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the bicyclooctane derivatives andcyclohexene alkyl and alkenyl carbinols and esters with, for example,gum arabic, gum tragacanth, carrageenan and the like, and thereafterspray-drying the resultant mixture whereby to obtain the particularsolid product. Pre-prepared flavor mixes in powder form, e.g., afruit-flavored powder mix, are obtained by mixing the dried solidcomponents, e.g., starch, sugar and the like, and bicyclooctanederivatives and cyclohexene alkyl and alkenyl carbinols and esters in adry blender until the requisite degree of uniformity is achieved.

It is presently preferred to combine with the bicyclooctane derivativesand cyclohexene alkyl and alkenyl carbinols and esters of our invention,the following adjuvants: Oil of Cubeb; Phellandrene; β-Phellandrene; Oilof Coriander; Oil of Pimento Leaf, Oil of Patchouli; Natural Lemon Oil;Acetaldehyde; α-Terpineol; Citral; Carvone; Terpinolene; α-Terpinene;Diphenyl; α-Fenchyl Alcohol; Cineole; Limonene; Linalool; GeranylAcetate; Nootkatone; Neryl Acetate; Heliotropin; Maltol, Vanillin; EthylMaltol; Ethyl Vanillin; Anisaldehyde; Alpha Pinene; Beta-Pinene;Beta-Caryophyllene; Dihydrocarveol; Piperonal; Piperine; Chavicine;Piperidine; Oil of Black Pepper; Black Pepper Oleoresin; Capsicum; Oilof Nutmeg; Cardamon Oil; Clove Oil; Separmint Oil; Oil of Peppermint;and C₁₀ -Terpinyl Ethers as described in Application for U.S. LettersPatent, Ser. No. 872,937 filed on Jan. 27, 1978, now U.S. Pat. No.4,131,687 issued on Dec. 26, 1978 (such as fenchyl ethyl ethers).

The oxabicyclooctane derivatives and the cyclohexene alkyl and alkenylcarbinols and esters of our invention can be used to contribute green,minty, herbaceous (e.g., rosemary, garden mint, thyme, wet lettuce),sweet, fruity, woody, minty, cooling-like, eucalyptol-like, buchu-like,caraway, spicey, carvone-like, basil-like, anise-like, citrus aromaswith minty, peppery and geranium-like and basil-blueberry-likeundertones to perfumes, perfumed articles and colognes. As olfactoryagents, the oxabicyclooctane derivatives and the cyclohexene alkyl andalkenyl carbinols and esters of our invention can be formulated into orused as components of a "perfume composition" or can be used ascomponents of a "perfumed article" or the perfume composition may beadded to perfumed articles.

The term "perfume composition" is used herein to mean a mixture oforganic compounds including, for example, alcohols, aldehydes, ketones,nitriles, ethers, lactones, natural essential oils, synthetic essentialoils and frequently hydrocarbons which are admixed so that the combinedodors of the individual components produce a pleasant or desiredfragrance. Such perfume compositions usually contain: (a) the main noteor the "bouquet" or foundation-stone of the composition; (b) modifierswhich round-off and accompany the main note; (c) fixatives which includeodorous substances which lend a particular note to the perfumethroughout all stages of evaporation, and substances which retardevaporation; and (d) top-notes which are usually low-boiling,fresh-smelling materials.

In perfume compositions, the individual component will contribute itsparticular olfactory characteristics, but the overall effect of theperfume composition will be the sum of the effects of each of theingredients. Thus, the individual compounds of this invention, ormixtures thereof, can be used to alter the aroma characteristics of aperfume composition, for example, by highlighting or moderating theolfactory reaction contributed by another ingredient in the composition.

The amount of the oxabicyclooctane derivatives and/or the cyclohexenealkyl and alkenyl carbinols and/or esters of this invention which willbe effective in perfume compositions depends on many factors, includingthe other ingredients, their amounts and the effects which are desired.It has been found that perfume compositions containing as little as 0.5%of the oxabicyclooctane derivatives and the cyclohexene alkyl and/oralkenyl carbinols and/or esters of this invention, or even less, can beused to impart an interesting minty, herbaceous and/or anise-like aromato soaps, liquid and solid cationic, anionic and nonionic detergents,cosmetics, powders, liquid and solid fabric softeners, opticalbrightener compositions, and other products. The amount employed canrange up to 50% or higher and will depend on considerations of cost,nature of the end product, and the effect desired on the finishedproduct and particular fragrance sought.

The oxabicyclooctane derivatives and the cyclohexene alkyl and alkenylcarbinols and esters of this invention can be used alone or in a perfumecomposition as an olfactory component in detergents and soaps, spaceodorants and deodorants; perfumes; colognes, toilet waters; bath salts;hair preparations such as lacquers, brilliantines, pomades, andshampoos; cosmetic preparations such as creams, deodorants, handlotions, and sun screens; powders such as talcs, dusting powders, facepowder, and the like. When used as an olfactory component of a perfumedarticle, as little as 0.01% of one or more of the oxabicyclooctanederivatives and/or cyclohexene alkyl and alkenyl carbinols and/or esterswill suffice to impart an interesting minty, herbaceous and/oranise-like aroma. Generally, no more than 0.5% is required.

In addition, the perfume composition can contain a vehicle or carrierfor the oxabicyclooctane derivatives and the cyclohexene alkyl andalkenyl carbinols and esters alone or with other ingredients. Thevehicle can be a liquid such as an alcohol such as ethanol, a glycolsuch as propylene glycol, or the like. The carrier can be an absorbentsolid such as a gum or components for encapsulating the composition suchas gelatin which can be used to form a capsule wall surrounding theperfume oil, by means of coacervation.

An additional aspect of our invention provides an organolepticallyimproved smoking tobacco product and additives therefor includingmethods of making the same which overcome problems heretoforeencountered in the creation or enhancement of specific desired naturaltobacco-like notes, particularly hay-like notes. Such notes, both priorto and on smoking, in both the main stream and the side stream, may nowbe readily controlled and maintained at the desired uniform levelregardless of variations in the tobacco components of the blend; or thenature of the filter used in conjunction with the smoking tobaccoarticle.

This invention further provides improved tobacco additives and additivesfor materials used in the fabrication of tobacco articles (particularlysmoking tobacco articles) and methods whereby desirable hay-like notesmay be imparted to smoking tobacco products and may be readily variedand controlled to produce the desired uniform flavoring characteristics.

In carrying out this aspect of our invention, we add to smoking tobaccomaterials or a suitable substitute therefor (e.g., dried lettuce leaves)an aroma and flavor additive containing as an active ingredient, one ormore of the oxabicyclooctane derivatives and/or the cyclohexene alkyland alkenyl carbinols and/or esters of our invention.

In addition to the oxabicyclooctane derivatives and the cyclohexenealkyl and alkenyl carbinols and esters of our invention, other flavoringand aroma additives may be added to the smoking tobacco material orsubstitute therefor either separately or in mixture with one or more ofthe oxabicyclooctane derivatives and/or the cyclohexene alkyl andalkenyl carbinols and/or esters of our invention:

I. Synthetic Materials

Beta-methylcinnamaldehyde;

Eugenol;

Dipentene;

Damascenone;

Maltol;

Ethyl maltol;

Delta-undecalactone;

Delta-decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate;

2-Hexen-1-ol;

2-Methyl-5-isopropyl-1,3-nonadiene-8-one;

2-Methyl-5-isopropylacetophenone;

2-Hydroxy-2,5,5,8α-tetramethyl-1-)2-hydroxyethyl)-decahydronaphthalene;

Dodecahydro-3α,6,6,9α-tetramethylnaphtho-(2,1-β)-furan;

4-Hydroxyhexenoic acid, gamma-lactone;

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No.3,589,372 issued on June 29, 1971

II. Natural Oils

Celery seed oil;

Coffee extract;

Bergamot oil;

Cocoa extract;

Nutmeg oil;

Origanum oil.

An aroma and flavoring concentrate containing one or more of theoxabicyclooctane derivatives and/or the cyclohexene alkyl and alkenylcarbinols and/or esters of our invention and, if desired, one or more ofthe above-indicated additional flavoring additives may be added to thesmoking tobacco material, to the filter or to the leaf or paper wrapperor to a filter which is part of the smoking article. The smoking tobaccomaterial may be shredded, cured, cased and blended tobacco material orreconstituted tobacco material or tobacco substitutes (e.g., lettuceleaves) or mixtures thereof. The proportions of flavoring additives maybe varied in accordance with taste, but insofar as enhancement or theimparting of hay-like notes prior to and on smoking, in both the mainstream and the side stream, we have found that satisfactory results areobtained if the proportion by weight of the sum total ofoxabicyclooctane derivatives and/or the cyclohexene alkyl and alkenylcarbinols and/or esters to smoking tobacco material is between 50 ppmand 1500 ppm (0.005%-0.15%) of the active ingredients to the smokingtobacco material. We have further found that satisfactory results areobtained if the proportions by weight of the sum total ofoxabicyclooctane derivatives and/or cyclohexene alkyl and alkenylcarbinols and/or esters used to flavoring material is between 0.05:1 and0.50:1.

Any convenient method for incorporating the oxabicyclooctane derivativesand cyclohexene alkyl and alkenyl carbinols and esters in the tobaccoproduct may be employed. Thus the oxabicyclooctane derivatives andcyclohexene alkyl and alkenyl carbinols and esters taken alone or alongwith other flavoring additives may be dissolved in a suitable solventsuch as food grade ethanol, pentane, diethyl ether and/or other volatileorganic solvents, and the resulting solution may either be sprayed onthe cured, cased and blended tobacco material; or the tobacco materialor filter may be dipped into such solution. Under certain circumstances,a solution of one or more oxabicyclooctane derivatives and/orcyclohexene alkyl and alkenyl carbinols and/or esters taken alone ortaken further together with other flavoring additives as set forthabove, may be applied by means of a suitable applicator such as a brushor roller on the paper or leaf wrapper for the smoking product, or itmay be applied to the filter by either spraying or dipping or coating.

Furthermore, it will be apparent that only a portion of the tobacco orsubstitute therefor need be treated, and the thus-treated tobacco may beblended with other tobaccos before the ultimate tobacco product isformed. In such cases, the tobacco treated may have one or moreoxabicyclooctane derivatives and/or cyclohexene alkyl and alkenylcarbinols and/or esters of our invention in excess of the amounts orconcentrations above indicated so that when blended with other tobaccos,the final product will have the percentage within the indicated range.

While our invention is particularly useful in the manufacture of smokingtobacco such as cigarette tobacco, cigar tobacco and pipe tobacco, othertobacco products formed from sheeted tobacco dust or fines may also beused. As stated supra, the oxabicyclooctane derivatives and cyclohexenealkyl and alkenyl carbinols and esters of our invention can beincorporated with materials such as filter tip materials, seam paste,packaging materials and the like which are used along with the tobaccoto form a product adapted for smoking. Furthermore, the oxabicyclooctanederivatives and cyclohexene alkyl and alkenyl carbinols and esters ofour invention can be added to certain tobacco substitutes of natural orsynthetic origin (e.g., dried lettuce leaves) and, accordingly, by theterm "tobacco" as used throughout this specification is meant anycomposition intended for human consumption, by smoking or otherwise,whether composed of tobacco plant parts or substitute materials or both.

It will thus be apparent that the oxabicyclooctane derivatives andcyclohexene alkyl and alkenyl carbinols and esters of our invention canbe utilized to alter, modify, augment or enhance sensory properties,particularly organoleptic properties, such as flavor(s) and/orfragrance(s) of a wide variety of consumable materials.

The following examples serve to illustrate our invention, and thisinvention is to be considered restricted thereto only as indicated inthe appended claims.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE I ##STR25## Part 1A: Preparation of2,4-Dimethyl-Alpha-Isopropyl-3-Cyclohexene-1-Methanol

A solution of isopropyl magnesium chloride in ether is prepared bydropwise adding a solution of 164 grams (2.1 moles) of 2-chloropropanein 200 ml of ether to a stirred slurry of 50 grams (2.1 moles) ofmagnesium in 500 ml of ether at reflux under nitrogen. The resultingsolution is stirred at reflux for 30 minutes. A solution of 164 grams (2moles) of 2,4-dimethyl-3-cyclohexenecarboxaldehyde in 200 ml of ether isadded over a 45-minute period to the reaction mixture at reflux undernitrogen. The resulting slurry is heated at reflux for 30 minutes andthen cooled to 0° C. 400 ml of 18% aqueous hydrochloric acid is slowlyadded with cooling and stirring. Two clear layers are formed. Theaqueous layer is discarded and the organic layer is washed twice with H₂O, neutralizing the second wash with aqueous caustic soda. The ether isremoved by distillation at atmospheric pressure. Fractional distillationof the remaining oil (375 grams) through a 11/2"×12" Goodloe packedcolumn affords 121 grams of recovered2,4-dimethyl-3-cyclohexenecarboxaldehyde; 54 grams of1,5-dimethyl-3-isopropyl-2-oxabicyclo[2.2.2]octane; and 173 grams of2,4-dimethylalpha-isopropyl-3-cyclohexene-1-methanol (b.p. 91° C., 2.1mm Hg pressure).

The GLC profile for the reaction mass is set forth in FIG. 1. The NMRspectrum for fraction 12 is set forth in FIG. 2. The infra-red spectrumfor fraction 12 is set forth in FIG. 3. The NMR and IR spectra confirmthat the resulting product is2,4-dimethyl-alphaisopropyl-3-cyclohexene-1-methanol.

Part IB: Preparation of1,5-Dimethyl-3-Isopropyl-2-Oxabicyclo[2.2.2]Octane

A solution of 130 grams of 2,4-dimethyl-alpha-isopropyl-3-cyclohexenemethanol, 300 grams of isopropyl alcohol and 1000 ml of concentrated HClis heated 21/2 hours at reflux. The reaction mass is cooled and 1500 mlof H₂ O and 100 ml of toluene is added with stirring. The aqueous layeris discarded and the organic layer is washed twice with water,neutralizing with aqueous caustic soda on the second wash. The organiclayer is distilled through a 48" Vigreux column affording 25 grams of1,5-dimethyl-3-isopropyl-2-oxabicyclo[2.2.2]octane (b.p. 55° C., 1.8 mmHg pressure).

The NMR and IR spectra is taken from fraction 5 of the distillation.

FIG. 4 is the GLC profile for the reaction product of this Example IB.FIG. 5 is the NMR spectrum for fraction 5. FIG. 6 is the infra-redspectrum for fraction 5.

EXAMPLE II Preparation of1-Methyl-3-(2-Methylpropyl)-2-Oxabicyclo[2.2.2]Octane ##STR26##

A solution of isobutyl magnesium bromide in ether is prepared bydropwise adding a solution of 517 grams (3.45 moles) of 1-bromo-2-methylpropane in 700 ml of dry ether to a stirred slurry of 76.5 grams ofmagnesium (3.15 moles) in 600 ml of dry ether under nitrogen at reflux.The resulting solution is stirred at reflux for 30 minutes. A solutionof 372 grams of 4-methyl-3-cyclohexenecarboxaldehyde (3.38 moles) in 200ml of ether is then added to the reaction mixture over a period of onehour at reflux under nitrogen. The resulting slurry is heated at refluxfor 30 minutes and then cooled to 0° C. 1200 grams of 20% sulfuric acidis slowly added with external cooling over a 30-minute period. After theaddition is complete, two clear layers appear. A distillation head isplaced on the flask and ether is distilled from the reaction mixture atatmospheric pressure to a pot temperature of 90° C. 500 ml of water and300 ml of isopropyl alcohol is added to the reaction mixture. Sulfuricacid (200 grams) is added slowly and the resulting solution is heated toreflux for 9 hours. At the end of this period, the reaction is cooled.500 ml of water and 200 ml of toluene is added thereto with stirring.The phases are allowed to separate and the aqueous phase is discarded.The organic phase is washed twice with H₂ O with sufficient sodiumcarbonate added to the second wash to adjust to pH to 7-8. Distillationof the organic layer affords 220 grams (1.2 moles) of1-methyl-3-(2-methylpropyl)-2-oxabicyclo[2.2.2]octane. Fractionationthrough a 1.5"×12" Goodloe column affords the pure compound (b.p. 62°C., 2.00 mm Hg pressure).

The NMR spectra and IR spectra show fraction 4 of the distillation.

The GLC profile for the reaction product is set forth in FIG. 7. The NMRspectrum for fraction 4 is set forth in FIG. 8. The infra-red spectrumfor fraction 4 is set forth in FIG. 9.

EXAMPLE III Preparation of4,6-Dimethyl-Alpha-Allyl-3-Cyclohexenemethanol ##STR27##

To a stirred slurry of 53 grams of magnesium (2.2 mole) and 500 ml ofdry tetrahydrofuran under nitrogen, is added dropwise a solution of 168grams (2.2 moles) of allyl chloride and 276 grams (2.0 moles) of4,6-dimethyl-3-cyclohexenecarboxaldehyde at reflux over a two-hourperiod. The reaction mixture is heated at reflux for 30 minutes,whereupon 400 ml of toluene is added. A distillation head is attached tothe reaction flask and the toluene is distilled at atmospheric pressureto a pot temperature of 114° C. The remaining solution is cooled to 0°C., whereupon 900 ml of 18% aqueous hydrochloric acid solution is slowlyadded with external cooling. Two clear layers are formed. The aqueouslayer is discarded and the organic layer is washed twice with water,neutralizing the second wash with caustic soda. The organic layer isquickly distilled. The distillate is fractionally redistilled through a1"×12" Goodloe packed column to afford 250 grams of4,6-dimethyl-alpha-allyl-3-cyclohexenemethanol (b.p. 102°, 3.2 mm Hgpressure).

The GLC profile for the reaction product produced in this example is setforth in FIG. 10. The NMR spectrum is set forth in FIG. 11. Theinfra-red spectrum is set forth in FIG. 12.

EXAMPLE IV Preparation of 2,4-Dimethyl-Alpha-Allyl-3-Cyclohexenemethanol##STR28##

To a stirred slurry of 53 grams of magnesium (2.2 mole) and 500 ml ofdry tetrahydrofuran, under nitrogen, is dropwise added a solution of 168grams (2.2 moles) of allyl chloride and 276 grams (2.0 moles) of4,6-dimethyl-3-cyclohexenecarboxaldehyde at reflux (67° C.) over atwo-hour period. The reaction mixture is heated to reflux for 30minutes, whereupon 400 ml of toluene is added. A distillation head isattached to the reaction flask and the tetrahydrofuran is distilled offat atmospheric pressure to a pot temperature of 114° C. The remainingsolution is cooled to 0° C., whereupon 900 ml of 18% hydrochloric acidsolution is slowly added with external cooling. Two clear layers areformed. The aqueous layer is discarded and the organic layer is quicklydistilled. The distillate is fractionally redistilled through a 1"×12"Goodloe packed column to afford 250 grams of4,6-dimethyl-alpha-allyl-3-cyclohexenemethanol (b.p. 88°, 2.0 mm Hgpressure).

The NMR spectrum is set forth in FIG. 13. The infra-red spectrum is setforth in FIG. 14.

EXAMPLE V ##STR29## Part V(A): Preparation ofAlpha-Allyl-4-Methyl-3-Cyclohexene Methanol

A solution of 251 grams (3.3 moles) of allyl chloride and 372 grams (3moles) of 4-methyl-3-cyclohexenecarboxaldehyde is added dropwise to astirred slurry of 77 grams of magnesium (3.2 moles) and 1500 ml oftetrahydrofuran at reflux under nitrogen over a three-hour period. Thereaction mixture is heated at reflux (71° C.) for 30 minutes after thefeed is complete, whereupon 500 ml of toluene is added. A distillationhead is attached to the reaction flask and the tetrahydrofuran isdistilled off at atmospheric pressure to a pot temperature of 100° C.The remaining organic solution is cooled to 0° C., whereupon 1000 ml of18% hydrochloric acid solution is slowly added with external cooling.Two clear layers is formed. The aqueous layer is discarded and theorganic layer is quickly distilled. The distillate is fractionallyredistilled through a 1.5"×12" Goodloe packed column to afford 325 gramsof alpha-allyl-4-methyl-3-cyclohexene methanol (b.p. 92° C., 3.0 mm Hgpressure).

The NMR spectrum is set forth in FIG. 15. The infra-red spectrum is setforth in FIG. 16.

Part V(B): Preparation of 3-Allyl-1-Methyl-2-Oxabicyclo[2.2.2]Octane

A solution of 848 grams of alpha-allyl-4-methyl-3-cyclohexenyl methanol,5 liters of water, 750 grams of sulfuric acid and 1000 grams ofisopropyl alcohol is heated to reflux for 24 hours. At the end of thisperiod an additional 750 grams of sulfuric acid is added and heating iscontinued for another 5 hours. At the end of this time, the reactionmass is cooled and 500 ml of toluene is added thereto. The organic layeris washed twice with water and fractionally distilled through a 1.5"×12"Goodloe packed column to afford 692 grams of3-allyl-1-methyl-2-oxabicyclo[2.2.2]octane (b.p. 68° C., 4 mm Hgpressure).

The NMR spectra and IR spectra consist of fraction 4.

The NMR spectrum for fraction 4 is set forth in FIG. 17. The infra-redspectrum for fraction 4 is set forth in FIG. 18.

EXAMPLE VI ##STR30## Part VI(A): Preparation ofAlpha-n-Butyl-2,4-Dimethyl-3-Cyclohexene Methanol

A solution of 782 grams (5.75 moles) of 1-bromobutane is added dropwiseover a three-hour period to a stirred slurry of 131 grams (5.4 moles) ofmagnesium in 1200 ml of dry ether under nitrogen at reflux. Theresulting solution is stirred at reflux for 1/2 hour. A solution of 690grams (5 moles) of 2,4-dimethyl-3-cyclohexenecarboxaldehyde in 400 ml ofether is added at reflux over a two-hour period. The resulting mixtureis stirred at reflux for 1/2 hour, whereupon it is cooled to 0° C. 1500ml of 17% hydrochloric acid solution is slowly added with externalcooling. Two clear layers is formed. The aqueous layer is discarded andthe organic layer is washed twice with water, neutralizing with aqueouscaustic soda on the second wash. Distillation through a 2" stone packedcolumn affords 850 grams of a mixture containingalpha-n-butyl-2,4-dimethyl-3-cyclohexene methanol and3-butyl-1,5-dimethyl-2-oxabicyclo[2.2.2]octane. Fractional distillationthrough a 1.5"×12" Goodloe packed column affords 346 grams ofalpha-n-butyl-2,4-dimethyl-3-cyclohexene methanol (b.p. 113° C., 1.8 mmHg pressure).

The GLC profile for the reaction product is set forth in FIG. 19.

Part VI(B): Preparation of3-n-Butyl-2,5-Dimethyl-2-Oxabicyclo[2.2.2]Octane

A solution of 746 grams of the reaction product of Example VI(A) in 1800ml water, 200 grams of sulfuric acid, 400 ml isopropyl alcohol, and 746grams of an oil consisting of a mixture ofalpha-n-butyl-2,4-dimethyl-3-cyclohexene methanol and3-butyl-2,5-dimethyl-2-oxabicyclo[2.2.2]octane is heated to reflux for 8hours. At the end of this time, the reaction mixture is cooled and 1liter of water and 400 ml of toluene is added thereto. The aqueous layeris discarded and the organic layer is washed twice with water,neutralizing the second wash with aqueous caustic soda. Distillationthrough a 1.5"×12" Goodloe column affords 533 grams of3-n-butyl-2,5-dimethyl-2-oxabicyclo[2.2.2]octane (b.p. 120° C., 4 mm Hgpressure).

FIG. 20 is the GLC profile of the reaction product thus produced. FIG.21 is the infra-red spectrum confirming that the substance produced is3-n-butyl-2,5-dimethyl-2-oxabicyclo[2.2.2]octane. ##STR31##

Part VII(A): Preparation of Alpha-n-Butyl-4,6-Dimethyl-3-CyclohexeneMethanol

A solution of 469 grams (3.45 moles) of 1-bromobutane in 400 ml of etheris added dropwise under nitrogen to a stirred slurry of 78 grams (3.2moles) of magnesium in 800 ml of ether under nitrogen. After theaddition is complete, the reaction mixture is heated at reflux for 30minutes. To the boiling mixture is added a solution of 474 grams (3moles) of 4,6-dimethyl-3-cyclohexenylcaboxaldehyde in 200 ml of dryether over a 90 minute period. After the addition, the reaction mixtureis heated at reflux for an additional 30 minutes (42° C.). The reactionmass is cooled to 0° C. and 750 ml of 33% aqueous acetic acid is addeddropwise with external cooling. Two clear layers are formed. The aqueouslayer is discarded and the organic layer is washed twice with water,neutralizing with aqueous bicarbonate on the second wash. Distillationthrough a 1.5"×12" Goodloe column affords 500 grams ofalpha-n-butyl-4,6-dimethyl-3-cyclohexene methanol (b.p. 93° C., 0.8 mmHg pressure).

The GLC profile for this reaction product is set forth in FIG. 22. TheNMR spectrum for alpha-n-butyl-4,6-dimethyl-3-cyclohexene methanol isset forth in FIG. 23. The infra-red spectrum for this compound is setforth in FIG. 24.

Part VII(B): Preparation of3-n-Butyl-1,5-Dimethyl-2-Oxabicyclo[2.2.2]Octane

A solution of 500 grams of alpha-n-butyl-4,6-dimethyl-3-cyclohexenemethanol, 600 grams of sulfuric acid, 1400 grams of water and 500 gramsof isopropyl alcohol is heated at reflux for 14 hours. The reaction massis cooled, diluted with 1500 ml of H₂ O and 200 ml of toluene. Theaqueous layer is discarded and the organic layer is washed twice withwater, neutralizing with aqueous sodium hydroxide on the second wash.Distillation through a 1.5"×12" Goodloe column affords 351 grams of3-n-butyl-1,5-dimethyl-2-oxabicyclo[2.2.2]octane (b.p. 90° C., 3 mm Hgpressure).

FIG. 25 is the GLC profile for this reaction product at the end of 5hours of reaction time. FIG. 26 is the NMR spectrum for the resultingreaction product. FIG. 27 is the infra-red spectrum for the resultingproduct, 3-n-butyl-1,5-dimethyl-2-oxabicyclo[2.2.2]octane.

EXAMPLE VIII Preparation of3-Isopropyl-1-Methyl-2-Oxabicyclo[2.2.2]Octane ##STR32##

A solution of isopropyl magnesium chloride in ether is prepared bydropwise adding a solution of 410 grams (3.45 moles) of isopropylchloride in 700 ml of dry ether to a stirred slurry of 76.5 grams ofmagnesium (3.15 moles) in 600 ml of dry ether under nitrogen at reflux.The resulting solution is stirred at reflux for 30 minutes. A solutionof 372 grams of 4-methyl-3-cyclohexenecarboxaldehyde (3.38 moles) in 200ml of ether is then added to the reaction mixture over a period of 1hour at reflux under nitrogen. The resulting slurry is heated at refluxfor 30 minutes and then cooled to 0° C. 1200 grams of 20% sulfuric acidis slowly added with external cooling over a 30 minute period. After theaddition is complete, two clear layers appear. A distillation head isplaced on the flask and ether is distilled from the reaction mixture atatmospheric pressure to a pot temperature of 90° C. 500 ml of water and300 ml of isopropyl alcohol is added to the reaction mixture. Sulfuricacid (200 grams) is added slowly and the resulting solution is heated toreflux for 9 hours. At the end of this period the reaction mass iscooled. 500 ml of water and 200 ml of toluene is added thereto withstirring. The phases are allowed to separate and the aqueous phase isdischarged. The organic phase is washed twice with H₂ O, with sufficientsodium carbonate added to the second wash to adjust to pH to 7-8.Distillation of the organic layer affords 255 grams of3-isopropyl-1-methyl-2-oxabicyclo[2.2.2]octane.

The NMR and IR spectra show fraction 10 of the distillation.

FIG. 28 is the GLC profile for the reaction product (Conditions: 180°isothermal; SE-30 column). The NMR spectrum for the resulting reactionproduct is set forth in FIG. 29. The infra-red spectrum for theresulting reaction product is set forth in FIG. 30.

EXAMPLE IX Preparation of1,5-Dimethyl-3-n-Propyl-2-Oxabicyclo[2.2.2]Octane ##STR33##

A solution of n-propyl magnesium bromide in ether is prepared bydropwise adding a solution of 469 grams (3.45 moles) of 1-bromopropanein 700 ml of dry ether to a stirred solution of 76.5 grams of magnesium(3.15 moles) in 600 ml of dry ether under nitrogen at reflux. Theresulting solution is stirred at reflux for 30 minutes. A solution of414 grams of 2,4 -dimethyl-3-cyclohexenecarboxaldehyde (3.38 moles) in200 ml of ether is then added to the reaction mixture over a period of 1hour at reflux under nitrogen. The resulting slurry is heated at refluxfor 30 minutes and then cooled to 0° C. 1200 grams of 20% sulfuric acidis slowly added with external cooling over a 30 minute period. After theaddition is complete, two clear layers appear. A distillation head isplaced on the flask and ether is distilled from the reaction mixture atatmospheric pressure to a pot temperature of 90° C. 500 ml of water and300 ml of isopropyl alcohol is added to the reaction mixture. Sulfuricacid (200 grams) is added slowly and the resulting solution is heated toreflux for 9 hours. At the end of this period, the reaction is cooled.500 ml of water and 200 ml of toluene is added thereto with stirring.The phases are allowed to separate and the aqueous phase is discarded.The organic phase is washed twice with H₂ O with sufficient sodiumcarbonate added to the second wash to adjust to pH to 7-8. Distillationof the organic layer affords 288 grams of2,4-dimethyl-3-n-propyl-2-oxabicyclo[2.2.2]octane.

The NMR and IR spectra represent fraction 10 of the distillation.

FIG. 31 is the GLC profile for the reaction product of this example.FIG. 32 is the NMR spectrum for the reaction product of this example,2,4-dimethyl-3-n-propyl-2-oxabicyclo[2.2.2]octane. FIG. 33 is theinfra-red spectrum for this reaction product.

EXAMPLE X Preparation of1,5-Dimethyl-3-n-Pentyl-2-Oxabicyclo[2.2.2]Octane ##STR34##

A solution of n-pentyl magnesium bromide in ether is prepared bydropwise adding a solution of 521 grams of 1-bromopentane in 700 ml ofether to a stirred slurry of 76.5 grams of magnesium in 600 ml of etherunder nitrogen at reflux. The resulting solution is stirred at refluxfor 30 minutes under nitrogen. A solution of 414 grams of2,4-dimethyl-3-cyclohexenylcarboxaldehyde in 200 ml of ether is thenadded to the reaction mass over a period of 1 hour at reflux undernitrogen. The resulting slurry is heated at reflux for 30 minutes andthen cooled to 0° C. 1150 grams of 25% acetic acid is slowly added withexternal cooling over a 30 minute period. After the addition iscomplete, two clear layers are obtained. A distillation head is placedon the flask and ether is distilled from the reaction mixture atatmospheric pressure and ether is distilled from the reaction mixture.Sulfuric acid (200 grams) is slowly added and the resulting solution isheated to reflux for 9 hours. At the end of this period, the reactionmass is cooled and 500 ml of water and 200 ml of toluene is addedthereto with stirring. Two clear phases are formed. The organic phase iswashed twice with water, with sufficient sodium carbonate added to thesecond wash to adjust to pH 7-8. Distillation of the organic phasethrough a short column affords 594 grams of a mixture ofalpha-n-pentyl-2,4-dimethyl-3-cyclohexenyl methanol,2,4-dimethyl-3-cyclohexenyl methanol and1,5-dimethyl-3-n-pentyl-2-oxabicyclo[2.2.2]octane. Fractionaldistillation afforded 182.5 grams of1,5-dimethyl-3-n-pentyl-2-oxabicyclo[2.2.2]octane (b.p. 83° C., 1.68 mmHg pressure).

The NMR and IR spectra are taken from fraction 7 of the distillation.

FIG. 34 is the GLC profile for the reaction product of this example.FIG. 35 is the NMR spectrum for fraction 7. FIG. 36 is the infra-redspectrum for fraction 7.

EXAMPLE XI Tomato Juice Formulations

The following tomato juice formulation is prepared by admixing thefollowing ingredients:

    ______________________________________                                        Ingredient              Parts by Weight                                       ______________________________________                                        Maltol                      2                                                 Vanillin                    20                                                Ethyl Vanillin              3                                                 Anisaldehyde (1% in Propylene                                                                             1                                                 Glycol)                                                                       Heliotropin (10% in Propylene                                                                             2                                                 Glycol)                                                                       Ethanol (95%)               12                                                Propylene Glycol            60                                                                   TOTAL    100                                               ______________________________________                                    

To a canned tomato juice (manufactured by Campbell Soup Company ofCamden, N.J.; ingredients: pure tomato juice, slightly salted) at therate of 2 ppm are added, one of the following ingredients:

(a) 1-methyl-3-(2-methylpropyl) -2-oxabicyclo[2.2.2]octane preparedaccording to Example II

(b) 3-n-butyl-2,5-dimethyl-2-oxabicyclo[2.2.2]octane

(c) 1,5-dimethyl-3-n-propyl-2-oxabicyclo[2.2.2]octane produced accordingto Example IX

(d) 1,5-dimethyl-3-n-pentyl-2-oxabicyclo[2.2.2]octane produced accordingto Example X

Each of the formulations with said 2-oxabicyclo[2.2.2]octaneindividually added is evaluated by a bench panel of three members. Thepanel concludes that in each of the cases (a), (b), (c) and (d), thespicey notes are increased with more black pepper notes added both inaroma and taste, and aftertaste in each of cases (a), (b), (c) and (d)being fuller and pleasantly longer lasting.

EXAMPLE XII Toothpaste Flavor Formulations

The following basic toothpaste flavor formulation is prepared:

    ______________________________________                                        Ingredients      Parts by Weight                                              ______________________________________                                        Cardamon Oil     0.2                                                          Clove Oil        1.0                                                          Spearmint Oil    2.0                                                          Peppermint Oil   96.8                                                         ______________________________________                                    

This flavor formulation is divided into three portions. Eight parts byweight of the first portion is combined with 2 parts by weight ofanethol. Eight parts by weight of the second portion of this flavor iscombined with 2 parts by weight of alpha-allyl-4-methyl-3-cyclohexenemethanol prepared according to Example V(A). Eight parts by weight ofthe third portion of this flavor is combined with 2 parts by weight of2,4-dimethyl-alpha-allyl-3-cyclohexene methanol prepared according toExample IV. Each of the three flavors are compared in water at the rateof 10 ppm and evaluated by a bench panel. Each of the three flavors havesweet anise-like character but the flavor containing the cyclohexenemethanol derivatives produced according to Example IV and according toExample V(A) produce, in addition, fuller licorice-related notes andalso have additional pleasant nuances; additional sweet, green andfennel notes in the case of use of the product produced according toExample V(A) and additional sweet, floral, fruity, berry-like and greennotes in the case of use of the material produced according to ExampleIV. Therefore, the flavors containing the2,4-dimethyl-alpha-allyl-3-cyclohexene methanol and also containing thealpha-allyl-4-methyl-3-cyclohexene methanol are each considered by thebench panel as being better and more suitable toothpaste flavors withunique flavor effects.

EXAMPLE XIII Lemon Flavor Formulation

The following lemon flavor formulation is prepared:

    ______________________________________                                        Ingredients          Parts by Weight                                          ______________________________________                                        Natural Lemon Oil, Terpeneless                                                                     10                                                       Acetaldehyde         0.6                                                      Alpha-terpineol      2.1                                                      Citral               1.8                                                      Carvone              0.24                                                     Terpinolene          1.2                                                      Alpha-terpinene      0.25                                                     Diphenyl             0.25                                                     Alpha Fenchyl Alcohol                                                                              0.25                                                     Limonene             0.35                                                     Linalool             0.25                                                     Geranyl Acetate      0.25                                                     Nootkatone           0.25                                                     Neryl Acetate        0.25                                                     ______________________________________                                    

The flavor formulation is divided into two portions. Four parts permillion of 3-isopropyl-1-methyl-2-oxabicyclo[2.2.2]octane preparedaccording to Example VIII is added to 200 parts per million of the firstportion of the lemon flavor prepared above; and to the second portion ofthe lemon flavor nothing is added. A definite aroma improvement, a morenatural lemon juice aroma and taste as well as a pleasant sour effectand generally improved taste with lime nuances is created as a result ofthe addition of the 3-isopropyl-1-methyl-2-oxabicyclo[2.2.2]octane tothe lemon flavor. In general, the3-isopropyl-1-methyl-2-oxabicyclo[2.2.2]octane supplies a natural "lemonjuice" note to this lemon flavor. The flavor is additionally improvedstill further with addition of 2 parts per million of fenchyl ethylether prepared according to application for U.S. Letters Patent, Ser.No. 872,937 filed on Jan. 27, 1978, now U.S. Pat. No. 4,131,687 issuedon Dec. 26, 1978.

EXAMPLE XIV A. Powder Flavor Formulation

20 Grams of the flavor composition of Example XIII is emulsified in asolution containing 300 gm gum acacia and 700 gm water. The emulsion isspray-dried with a Bowen Lab Model Drier utilizing 260 c.f.m. of airwith an inlet temperature of 500° F., an outlet temperature of 200° F.and a wheel speed of 50,000 rpm.

B. Sustained Release Flavor

The following mixture is prepared:

    ______________________________________                                        Ingredients            Parts by Weight                                        ______________________________________                                        Liquid Lemon Flavor                                                           Composition of Example XIII                                                                          20                                                     Propylene glycol       9                                                      Cab-O-Sil ® M-5    5.00                                                   (Brand of Silica produced by the                                              Cabot Corporation of 125 High Street,                                         Boston, Mass. 02110;                                                          Physical Properties:                                                          Surface Area: 200 m.sup.2 gm                                                  Nominal particle size: 0.012 microns                                          Density: 2.3 lbs/cu.ft.)                                                      ______________________________________                                    

The Cab-O-Sil is dispersed in the liquid lemon flavor compositions ofExample XIII with vigorous stirring, thereby resulting in a viscousliquid. 71 Parts by weight of the powder flavor composition of Part A,supra, is then blended into the said viscous liquid, with stirring, at25° C. for a period of 30 minutes resulting in a dry, free flowingsustained release flavor powder.

EXAMPLE XV

10 Parts by weight of 50 Bloom pigskin gelatin is added to 90 parts byweight of water at a temperature of 150° F. The mixture is agitateduntil the gelatin is completely dissolved and the solution is cooled to120° F. 20 Parts by weight of the liquid flavor composition of ExampleXIII is added to the solution which is then homogenized to form anemulsion having particle size typically in the range of 2-5 microns.This material is kept at 120° F. under which conditions the gelatin willnot jell.

Coacervation is induced by adding slowly and uniformly 40 parts byweight of a 20% aqueous solution of sodium sulphate. During coacervationthe gelatin molecules are deposited uniformly about each oil droplet asa nucleus.

Gelation is effected by pouring the heated coacervate mixture into 1,000parts by weight of 7% aqueous solution of sodium sulphate at 65° F. Theresulting jelled coacervate may be filtered and washed with water attemperatures below the melting point of gelatin, to remove the salt.

Hardening of the filtered cake, in this example, is effected by washingwith 200 parts by weight of 37% solution of formaldehyde in water. Thecake is then washed to remove residual formaldehyde. EXAMPLE XVI

Chewing Gum

100 Parts by weight of chicle are mixed with 4 parts by weight of theflavor prepared in accordance with Example XIV. 300 Parts of sucrose and100 parts of corn syrup are added. Mixing is effected in a ribbonblender with jacketed side walls of the type manufactured by the BakerPerkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant, long lastingsour lemon flavor.

EXAMPLE XVII Chewing Gum

100 Parts by weight of chicle are mixed with 18 parts by weight of theflavor prepared in accordance with Example XV. 300 Parts of sucrose and100 ml of corn syrup are then added. Mixing is effected in a ribbonblender with jacketed side walls of the type manufactured by the BakerPerkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant, long lastingsour lemon flavor.

EXAMPLE XVIII Toothpaste Formulation

The following separate groups of ingredients are prepared:

    ______________________________________                                        Parts by Weight   Ingredient                                                  ______________________________________                                        Group "A"                                                                     30.200            Glycerine                                                   15.325            Distilled Water                                              .100             Sodium Benzoate                                              .125             Saccharin Sodium                                             .400             Stannous Fluoride                                           Group "B"                                                                     12.500            Calcium Carbonate                                           37.200            Dicalsium Phosphate                                                           (Dihydrate)                                                 Group "C"                                                                      2.000            Sodium N-Lauroyl                                                              Sarcosinate (foaming                                                          agent)                                                      Group "D"                                                                      1.200            Flavor Material of                                                            Example XIV                                                 100.00 - TOTAL                                                                ______________________________________                                    

Procedure:

1. The ingredients in Group "A" are stirred and heated in a steamjacketed kettle to 160° F.

2. Stirring is continued for an additional three to five minutes to forma homogeneous gel

3. The powders of Group "B" are added to the gel, while mixing, until ahomogeneous paste is formed

4. With stirring, the flavor of "D" is added and lastly thesodium-n-lauroyl sarcosinate

5. The resultant slurry is then blended for one hour. The completedpaste is then transferred to a three roller mill and then homogenized,and finally tubed.

The resulting toothpaste when used in a normal toothbrushing procedureyields a pleasant lemon flavor, of constant strong intensity throughoutsaid procedure (1-1.5 minutes).

EXAMPLE XIX Chewable Vitamin Tablets

The flavor material produced according to the process of Example XIV isadded to a Chewable Vitamin Tablet. Formulation at a rate of 10 gm/Kgwhich Chewable Vitamin Tablet formulation is prepared as follows:

In a Hobart Mixer, the following materials are blended to homogeneity:

    ______________________________________                                                            Gms/1000 Tablets                                          ______________________________________                                        Vitamin C (ascorbic acid) as                                                  ascorbic acid-sodium ascorbate                                                mixture 1:1           70.11                                                   Vitamin B.sub.1 (thiamine mononitrate)                                        as Rocoat ® thiamine mononitrate                                          331/3% (Hoffman La Roche)                                                                           4.0                                                     Vitamin B.sub.2 (riboflavin) as                                               Rocoat ® riboflavin 331/3%                                                                      5.0                                                     Vitamin B.sub.6 (pyridoxine hydrochloride)                                    as Rocoat® pyridoxine hydrochloride                                       331/3%                4.0                                                     Niacinamide as Rocoat ® niacinamide                                       331/3%                33.0                                                    Calcium pantothenate  11.5                                                    Vitamin B.sub.12 (cyanocobalamin) as                                          Merck 0.1% in gelatin 3.5                                                     Vitamin E (dl-alpha tocopheryl                                                acetate) as dry Vitamin E acetate                                             331/3%                6.6                                                     d-Biotin              0.044                                                   Flavor of Example XIV (as indicated above)                                    Certified lake color  5.0                                                     Sweetener - sodium saccharin                                                                        1.0                                                     Magnesium stearate lubricant                                                                        10.0                                                    Mannitol q.s. to make 500.0                                                   ______________________________________                                    

Preliminary tablets are prepared by slugging with flat-faced punches andgrinding the slugs to 14 mesh. 13.5 gm dry Vitamin A Acetate and 0.6 gmVitamin D are then added as beadlets. The entire blend is thencompressed using concave punches at 0.5 gm each.

Chewing of the resultant tablets yields a pleasant, long-lasting,consistently strong lemon flavor with lime nuances for a period of 12minutes.

EXAMPLE XX Chewing Tobacco

Onto 100 pounds of tobacco for chewing (85% Wisconsin leaf and 15%Pennsylvania leaf) the following casing is sprayed at a rate of 30%:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        Corn Syrup            60                                                      Licorice              10                                                      Glycerine             20                                                      Fig Juice             4.6                                                     Prune Juice           5                                                       Alpha-allyl-4-methyl-3-cyclohexene                                            methanol prepared according to                                                Example V(A)          0.04                                                    ______________________________________                                    

The resultant product is redried to a moisture content of 20%. Onchewing, this tobacco has an excellent substantially consistent,long-lasting licorice nuance in conjunction with the tobacco notes.

EXAMPLE XXI

A tobacco is made up by mixing the following materials:

    ______________________________________                                        Ingredient        Parts by Weight                                             ______________________________________                                        Bright            40.1                                                        Burley            24.9                                                        Maryland          1.1                                                         Turkish           11.6                                                        Stem (flue cured) 14.2                                                        Glycerine         2.8                                                         Water             5.3                                                         ______________________________________                                    

The above tobacco is used in producing cigarettes, and the followingformulation is compounded and incorporated into each of thesecigarettes:

    ______________________________________                                        Ingredient        Parts by Weight                                             ______________________________________                                        Ethyl butyrate    .05                                                         Ethyl valerate    .05                                                         Maltol            2.00                                                        Cocoa extract     26.00                                                       Coffee extract    10.00                                                       Ethyl alcohol     20.00                                                       Water             41.90                                                       ______________________________________                                    

The above flavor is incorporated into model "filter" cigarettes at therate of 0.1%. One-third of these model cigarettes are treated in thetobacco section with 1,5-dimethyl-3-n-pentyl-2-oxabicyclo[2.2.2]octaneproduced according to Example X at 100 ppm per cigarette. Anotherone-third of these model cigarettes are treated in the filter with1,5-dimethyl-3-n-pentyl-2-oxabicyclo[2.2.2]octane produced according toExample X at the rate of 2×10⁻⁵ gm. When evaluated by paired comparison,the cigarettes treated both in the tobacco and in the filter with the1,5-dimethyl-3-n-pentyl-2-oxabicyclo[2.2.2]octane are found, in smokeflavor, to be more tobacco-like with enhanced hay, fruity, herbaceousnuances.

EXAMPLE XXII

The following mixture is prepared:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        Phenylacetic acid     70.0                                                    Coumarin              20.0                                                    Phenylethylphenyl acetate                                                                           100.0                                                   Phenyl ethyl alcohol  5.0                                                     Benzyl benzoate       100.0                                                   Dimethylphenylethyl carbinol                                                                        10.0                                                    Methyl anthranilate   5.0                                                     Beta ionone           10.0                                                    In the alternative, 1,5-dimethyl-                                             3-isopropyl-2-oxabicyclo[2.2.2]                                               octane produced according to                                                  Example I(B) or 3-allyl-1-                                                    methyl-2-oxabicyclo[2.2.2]octane                                              prepared according to Example                                                 V(B)                  30.0                                                    ______________________________________                                    

The 1,5-dimethyl-3-isopropyl-2-oxabicyclo[2.2.2]octane preparedaccording to Example I (B) imparts the green, minty, cooling effect tothis honey fragrance while also giving it a warm, herbaceous undertoneof a rosemary character.

The 3-allyl-1-methyl-2-oxabicyclo[2.2.2]octane prepared according toExample V (B) imparts the minty, eucalyptol-like, buchu-like andcaraway-like aroma nuances to this honey formulation while at the sametime giving it a warm, herbaceous (garden mint, thyme-like) aroma.

EXAMPLE XXIII Preparation of a Cosmetic Powder Composition

A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcumpowder with 0.25 g of the perfume composition prepared according toExample XXII. It has an excellent minty, green, herbaceous aroma.

EXAMPLE XXIV Perfumed Liquid Detergent

Concentrated liquid detergents (Lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818 issued onApr. 6, 1976) with green, minty, herbaceous aroma nuances are preparedcontaining 0.10%, 0.15% and 0.20% of the fragrance prepared according toExample XXII. They are prepared by adding and homogeneously mixing theappropriate quantity of fragrance formulation prepared according toExample XXII in the liquid detergent. The detergents all possessexcellent green, minty, herbaceous aromas, the intensity increasing withgreater concentrations of perfume composition of Example XXII.

EXAMPLE XXV Preparation of a Cologne and Handkerchief Perfume

The composition prepared according to Example XXII is incorporated intoa cologne at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, and5.0% in 85% aqueous food grade ethanol; and into a handkerchief perfumeat concentrations of 15%, 20%, 25%, and 30% (in 95% aqueous food gradeethanol). A distinctive and definite green, herbaceous, minty aroma isimparted to the cologne and to the handkerchief perfume at all levelsindicated above.

EXAMPLE XXVI Preparation of Soap Composition

One hundred grams of soap chips are mixed with one gram of each of theformulations of Example XXII until homogeneous compositions areobtained. In each of the cases, the homogeneous compositions are heatedunder three atmospheres pressure at 180° C. for a period of three hoursand the resulting liquids are placed into soap molds. The resulting soapcakes, on cooling, manifest green, minty, herbaceous aroma.

EXAMPLE XXVII Preparation of a Solid Detergent Composition

A detergent is prepared from the following ingredients according toExample I of Canadian Pat. No. 1,007,948:

    ______________________________________                                                           Percent by Weight                                          ______________________________________                                        "Neodol 45-11" (a C.sub.14 -C.sub.15                                          alcohol ethoxylated with                                                      11 moles of ethylene oxide)                                                                        12                                                       Sodium carbonate     55                                                       Sodium citrate       20                                                       Sodium sulfate, water                                                                              q.s.                                                     brighteners                                                                   ______________________________________                                    

This detergent is a "phosphate-free" detergent. A total of 100 grams ofthis detergent is admixed with 0.15 grams of each of the honey baseperfumes of Example XXII. Each of the detergent samples has an excellentgreen, minty, herbaceous aroma, the minty and herbaceous aromas beingimparted by the oxybicyclo[2.2.2]octanes prepared according to ExamplesI and V (B).

EXAMPLE XXVIII Preparation of a Cosmetic Powder Composition

A cosmetic powder is prepared by admixing in a ball mill, 100 g oftalcum powder with 0.25 g of 3-allyl-1-methyl-2-oxabicyclo[2.2.2]-octaneprepared according to Example V (B) and 0.25 g of1,5-dimethyl-3-isopropyl-2-oxabicyclo[2.2.2]octane prepared according toExample I (B). The resulting cosmetic powder has an excellent green,minty, herbaceous, buchu-like, caraway-like aroma with a cooling effectand garden mint, thyme and rosemary nuances.

EXAMPLE XXIX Perfumed Liquid Detergent

Concentrated liquid detergents (Lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818 issued onApr. 6, 1976) with green, minty, herbaceous, eucalpytol-like, buchu-likeand caraway aroma notes and rosemary, garden mint, and thyme undertonesand having a cooling effect are prepared containing 0.10%, 0.15%, 0.20%,and 0.25% of a 50-50 mixture of1,5-dimethyl-3-isopropyl-2-oxabicyclo[2.2.2]octane prepared according toExample I (B) and 3-allyl-1-methyl-2-oxabicyclo[2.2.2]-octane preparedaccording to Example V (B). They are prepared by adding andhomogeneously mixing the appropriate quantity of the mixture of1,5-dimethyl-3-isopropyl-2-oxabicyclo[2.2.2]octane and3-allyl-1-methyl-2-oxabicyclo[2.2.2]octane in the liquid detergent. Thedetergents all possess green, minty, herbaceous, eucalyptol-like,bucch-like and caraway-like aroma nuances with rosemary, garden mint andthyme undertone and a cooling effect, the intensity of each of theforegoing characteristics increasing with greater concentrations of50-50 mixture of 1,5-dimethyl-3 -isopropyl-2-oxabicyclo[2.2.2]octane and3-allyl-1-methyl-2-oxabicyclo[2.2.2]octane.

EXAMPLE XXX Preparation of Colognes and Handkerchief Perfumes

3-Allyl-1-methyl-2-oxabicyclo[2.2.2]octane prepared according to ExampleV (B) is incorporated into colognes at concentrations of 2.0%, 2.5%,3.0%, 3.5%, 4.0% and 4.5% in 85% aqueous food grade ethanol; and intohandkerchief perfumes at concentrations of 15%, 20%, 25% and 30% (in 95%aqueous ethanol). Distinctive minty, eucalyptol-like, herbaceous,buchu-like and caraway aroma nuances with garden mint and thymeundertones are imparted to the colognes and to the handkerchief perfumesat the various above levels indicated.

EXAMPLE XXXI Preparation of Colognes and Handkerchief Perfumes

1,5-Dimethyl-3-isopropyl-2-oxabicyclo[2.2.2]octane prepared according toExample I (B) is incorporated into colognes at concentrations of 2.0%,2.5%, 3.0%, 3.5%, 4.0% and 4.5% in 90% aqueous food grade ethanol; andinto handkerchief perfumes at concentrations of 15%, 20%, 25% (in 95%aqueous food grade ethanol). Distinctive and definitive green, minty,herbaceous aroma nuances with a rosemary type undertone and a coolingeffect are imparted to the colognes and to the handkerchief perfumes atthe above-indicated levels.

EXAMPLE XXXII Preparation of α-Allyl-4,6-Dimethyl-3-CyclohexenylmethylAcetate ##STR35##

A solution of 101 grams (0.56 moles) ofα-allyl-4,6-dimethyl-3-cyclohexenylmethanol and 102 grams of aceticanhydride are heated at reflux (135° C.) for two hours. The reactionmass is cooled to 50° C. and 700 ml of water and 100 ml of toluene areadded thereto. The mass is stirred for one hour. The aqueous layer isdiscarded and the organic layer is washed with water and dilute aqueoussodium bicarbonate respectively. Distillation through a 48" Vigreuxcolumn affords 91 grams of α-allyl-4,6-dimethyl-3-cyclohexenylmethylacetate (boiling point 107° C., mm Hg).

FIG. 37 sets forth the NMR spectrum for fraction 4 resulting from thisdistillation. FIG. 38 sets forth the infra-red spectrum for fraction 4resulting from this distillation.

EXAMPLE XXXIII Preparation of α-Allyl-2,4-Dimethyl-3-CyclohexenylmethylAcetate ##STR36##

A solution of 156 grams of α-allyl-2,4-dimethyl-3-cyclohexenylmethanoland 172 grams of acetic acid are heated at reflux for a period of twohours. The reaction mass is then cooled to 50° C. and 2 liters of waterand 100 ml of toluene are added thereto. The reaction mass is stirredfor a period of one hour. The aqueous layer is discarded and the organiclayer is washed with water and dilute aqueous sodium carbonaterespectively. Distillation through a 1"×12" Vigreux column affords 162grams of α-allyl-2,4-dimethyl-3-cyclohexenylmethyl acetate (boilingpoint 84° C., 0.8 mm Hg).

FIG. 39 sets forth the GLC profile for the crude reaction mass(Conditions: 180° C. isothermal, 10% SE-30 column).

FIG. 40 sets forth the NMR spectrum for the reaction product producedaccording to this example. FIG. 41 sets forth the infra-red spectrum forthe reaction product produced according to this example.

EXAMPLE XXXIV Preparation of α-Allyl-4-Methyl-3-CyclohexenylmethylAcetate ##STR37##

A solution of 195 grams (1.2 moles) ofα-allyl-4-methyl-3-cyclohexenylmethanol and 200 grams of aceticanhydride are heated to reflux (138° C.) for 2.5 hours. The reactionmass is cooled to 50° C. and two liters of water and 200 ml of tolueneare added thereto. The reaction mass is stirred for a period of 30minutes. The aqueous layer is discarded and the organic layer is washedsuccessively with 1 liter of water and 1 liter of dilute aqueous sodiumbicarbonate. The reaction mass is then stripped of toluene affording 229grams of an oil. This oil is distilled through a 1"×12" Goodloe packedcolumn to afford 194 grams of α-allyl-4-methyl-3-cyclohexenylmethylacetate (boiling point 99° C., 3 mm Hg).

The NMR spectrum for fraction 6 resulting from the above distillation isset forth in FIG. 43.

The infra-red spectrum for fraction 6 resulting from the abovedistillation is set forth in FIG. 44.

FIG. 42 sets forth the GLC profile for the crude reaction product(Conditions: 200° C. isothermal, 10% SE-30 packed column).

EXAMPLE XXXV

Utilizing the procedure of Example I of column 15 of U.S. Pat. No.3,632,396, a nonwoven cloth substrate useful as a dryer-addedfabric-softening article of manufacture is prepared wherein thesubstrate, the substrate coating and the outer coating and the perfumingmaterial are as follows:

1. a water "dissolvable" paper ("Dissolvo Paper");

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. an outer coating having the following formulation (m.p. about 150°F.):

57 percent C₂₀₋₂₂ HAPS

22 percent isopropyl alcohol

20 percent antistatic agent

1 percent of the oxabicyclooctane derivative or cyclohexyl alkyl oralkenyl carbinol or ester thereof of our invention as set forth in theTable I below and giving rise to the aroma nuances as set forth in saidTable I below:

                  TABLE I                                                         ______________________________________                                                         FRAGRANCE                                                    NAME OF COMPOUND CHARACTERISTICS                                              ______________________________________                                        1,5-Dimethyl-3-  A green, minty, herbaceous                                   isopropyl-2-oxabicyclo                                                                         (rosemary) aroma with a                                      [2.2.2]octane    cooling effect.                                              3-allyl-1-methyl-2-                                                                            A minty, eucalyptol-like,                                    oxabicyclo[2.2.2]                                                                              herbaceous (garden mint,                                     octane           thyme), buchu-like aroma                                                      with caraway-like nuances.                                   3-n-butyl-2,5-dimethyl-                                                                        A green, spicey, carvone-                                    2-oxabicyclo[2.2.2]                                                                            like aroma.                                                  octane                                                                        1,5-dimethyl-3-n-propyl-                                                                       A herbaceous, minty                                          2-oxabicyclo[2.2.2]                                                                            (garden mint) aroma with                                     octane           basil, thyme and caraway                                                      nuances.                                                     1,5-dimethyl-3-n-pentyl-                                                                       An oily, green, herbaceous                                   2-oxabicyclo[2.2.2]                                                                            (wet lettuce) aroma.                                         octane                                                                        α-allyl-4-methyl-3-                                                                      A sweet, anise, carvone-                                     cyclohexenemethanol                                                                            like and minty aroma.                                        2,4-dimethyl-α-allyl-                                                                    A sweet, anisic, citrus                                      3-cyclohexenemethanol                                                                          aroma with minty, peppery,                                                    and geranium-like under-                                                      tones.                                                       α-allyl-4-methyl-3-                                                                      A sweet, fruity, herbaceous,                                 cyclohexene-1-methanol                                                                         floral aroma with carvone-                                   acetate          like and geranyl acetate-                                                     like nuances.                                                4,6-dimethyl-α-allyl-                                                                    A sweet, herbaceous,                                         3-cyclohexenemethanol                                                                          fruity aroma with basil                                                       and blueberry-like under-                                                     tones.                                                       α-allyl-4,6-dimethyl-                                                                    A green fruity, anisic,                                      3-cyclohexene-1-methanol                                                                       woody aroma.                                                 acetate                                                                                        A green, floral, minty,                                                       lemonly aroma.                                               ______________________________________                                    

Fabric-softening compositions prepared as set forth above having theabove aroma characteristics essentially consist of a substrate having aweight of about 3 grams per 100 square inches, a substrate coating ofabout 1.85 grams per 100 square inches of substrate and an outer coatingof about 1.4 grams per 100 square inches of substrate, thereby providinga total aromatized substrate and outer coating weight ratio of about 1:1by weight of the substrate. The aromas as set forth in Table I above areimparted in a pleasant manner to the head space in the dryer onoperation thereof using the said dryer added fabric softening nonwovenfabric.

EXAMPLE XXXVI

A liquid detergent composition is prepared according to Example IV ofUnited Kingdom Pat. No. 1,498,520 whereby the following ingredients areadmixed:

    ______________________________________                                        Ingredient              Weight %                                              ______________________________________                                        Coconut alcohol ethoxylate                                                                            30%                                                   Linear alkyl benzene sulfonate,                                               triethanolamine salt (alkyl = C.sub.11.8                                      avg.)                   10%                                                   Potassium chloride      3%                                                    Triethanolamine         3%                                                    Triethanolammonium citrate                                                                            2%                                                    Ethyl alcohol           5%                                                    Soil release ether "D"  1.0%                                                  Oxabicyclooctane derivative or                                                cyclohexene alkyl or alkenyl                                                  carbinol and ester thereof of our                                             invention as set forth in Table II                                                                    3.0%                                                  Water                   Balance                                               ______________________________________                                    

The soil release ether "D" is defined according to Table II on page 15of United Kingdom Pat. No. 1,498,520.

This composition is prepared by admixing all of the ingredientsexclusive of soil release ether "D" and agitating the mixture until allelectrolytes are dissolved. Soil release ether "D" is then admixed withthe solution in the form of a dry powder which passes through 150 meshstandard sieve. The resulting composition is in the liquid state andeasily pourable. The composition is found not to redden on contact withplastic bottles, does not gel when diluted with water and has along-lasting aroma composition as defined in the following Table II whenthe following oxabicyclooctane derivatives or cyclohexene alkyl oralkenyl carbinols or esters thereof are added thereto:

                  TABLE II                                                        ______________________________________                                                          FRAGRANCE                                                   NAME OF COMPOUND  CHARACTERISTICS                                             ______________________________________                                        1,5-Dimethyl-3-   A green, minty, herbaceous                                  isopropyl-2-oxabicyclo                                                                          (rosemary) aroma with a                                     [2.2.2]octane     cooling effect.                                             3-allyl-1-methyl-2-                                                                             A minty, eucalyptol-like,                                   oxabicyclo[2.2.2] herbaceous (garden mint,                                    octane            thyme), buchu-like aroma                                                      with caraway-like nuances.                                  3-n-butyl-2,5-dimethyl-                                                                         A green, spicey, carvone-                                   2-oxabicyclo[2.2.2]                                                                             like aroma.                                                 octane                                                                        1,5-dimethyl-3-n-propyl-                                                                        A herbaceous, minty                                         2-oxabicyclo[2.2.2]                                                                             (garden mint) aroma with                                    octane            basil, thyme and caraway                                                      nuances.                                                    1,5-dimethyl-3-n-pentyl-                                                                        An oily, green, herbaceous                                  2-oxabicyclo[2.2.2]                                                                             (wet lettuce) aroma.                                        octane                                                                        α-allyl-4-methyl-3-                                                                       A sweet, anise, carvone-                                    cyclohexenemethanol                                                                             like and minty aroma.                                       2,4-dimethyl-α-allyl-                                                                     A sweet, anisic, citrus                                     3-cyclohexenemethanol                                                                           aroma with minty, peppery,                                                    and geranium-like under-                                                      tones.                                                      α-allyl-4-methyl-3-                                                                       A sweet, fruity, herbaceous,                                cyclohexene-1-methanol                                                                          floral aroma with carvone-                                  acetate           like and geranyl acetate-                                                     like nuances.                                               4,6-dimethyl-α-allyl-                                                                     A sweet, herbaceous,                                        3-cyclohexenemethanol                                                                           fruity aroma with basil                                                       and blueberry-like under-                                                     tones.                                                      α-allyl-4,6-dimethyl-                                                                     A green, fruity, anisic,                                    3-cyclohexene-1-methanol                                                                        woody aroma.                                                acetate                                                                                         A green, floral, minty,                                                       lemonly aroma.                                              ______________________________________                                    

This composition is added to an aqueous laundrying bath at aconcentration of 0.20% (weight) at a temperature of 55° C., waterhardness 7 grains/gallon and a pH of 10.0. Polyester and mixedpolyester/cotton fabrics are laundered in the bath for a period of 10minutes after which the fabrics are thoroughly rinsed with fresh waterand dried at ambient temperatures. The fabrics are provided with a soilrelease finish. The head space above the fabrics has a pleasant faintaroma as indicated in Table II above.

What is claimed is:
 1. A process for preparing oxabicycloalkanescomprising the steps of (i) reacting an alpha-beta unsaturated aldehydewith a conjugated 1,3-diene whereby a cyclohexene carboxaldehyde isformed; (ii) reacting the cyclohexene carboxaldehyde with an alkyl oralkenyl Grignard reagent; (iii) reacting the thus formed cyclohexenylcarbinol organometallic salt with water in the presence of a protonicacid to form the cyclohexenyl carbinol; (iv) cyclizing the resultingcyclohexenyl carbinol to form the oxabicyclooctane in the presence of acyclizing agent, said cyclization reaction taking place at a temperaturein the range of from 25° C. up to 150° C. in the presence of a protonicacid or a Lewis acid, and in the presence of an organic solvent miscibletherewith, according to the reaction sequence: ##STR38## wherein R₁ andR₃ each represent hydrogen or methyl and are each the same or different;wherein R₄ is hydrogen, methyl or ethyl; wherein R₂ is one of C₁ -C₆alkyl or one of C₃ -C₅ alkenyl; and wherein one of the dashed lines is acarbon-carbon double bond and the other of the dashed lines is acarbon-carbon single bond; and where X is chloro, bromo or iodo.